Role of organic and black carbon in the chemical composition of atmospheric aerosol at European background sites

The mass concentrations of inorganic ions, water-soluble organic carbon, water-insoluble organic carbon and black carbon were determined in atmospheric aerosol collected at three European background sites: (i) the Jungfraujoch, Switzerland (high-alpine, PM_2.5 aerosol); (ii) K-puszta, Hungary (rural, PM_1.0 aerosol); (iii) Mace Head, Ireland (marine, total particulate matter). At the Jungfraujoch and K-puszta the contribution of carbonaceous compounds to the aerosol mass was higher than that of inorganic ions by 33% and 94%, respectively. At these continental sites about 60% of the organic carbon was water soluble, 55–75% of the total carbon proved to be refractory and a considerable portion of the water soluble, refractory organic matter was composed of humic-like substances. At Mace Head the mass concentration of organic matter was found to be about twice than that of nonsea-salt ions, 40% of the organic carbon was water soluble and the amount of highly refractory carbon was low. Humic-like substances were not detected but instead low molecular weight carboxylic acids were responsible for about one-fifth of the water-soluble organic mass. These results imply that the influence of carbonaceous compounds on aerosol properties (e.g. hygroscopic, optical) might be significant.     

Validation of trajectory statistical methods

A number of works have been trying to validate various trajectory statistical methods (TSMs), mostly through subjective comparison with known sources. Here in a more comprehensive and quantitative approach three trajectory statistical methods (potential source contribution function (PSCF), concentration field method (CF), and redistributed concentration field method (RCF)) were subjected to two validation approaches: validation with virtual and real sources under idealised conditions, where the effects of dispersion and removal of the trace substance are excluded, and comparisons with the EMEP SO₂ emission inventory under realistic conditions.The best performance was achieved in an idealised situation with about 78% common spatial variance between the EMEP emission inventory and the trajectory statistical reconstruction of the EMEP emission inventory with the RCF method, whereas the real world experiments for SO₂ on an European scale resulted in a much lower performance with 33% common spatial variance between the EMEP SO₂ emission inventory and the trajectory statistical reconstruction with the PSCF method.The experiments suggest that the limitation of the accuracy and spatial range of TSMs are rooted in the simplified transport process described just by trajectory paths. If one links these limitations with the concept of the mean residence time of the considered trace substance, a temporal and spatial scope can be deduced, within which the effect of the simplification of the transport process is restricted and useful information can be expected from TSMs. The lower values of the mean residence time for SO₂ range from 9 to 17 h, which were deduced from the decay approach, where an exponential decay, respectively, removal of SO₂ was built into the trajectory statistical procedure. The values derived from the optimum real world validation experiment place the upper range of the mean residence time to about 60 h or 2.5 days. Both figures are within the range of mean residence times for SO₂ cited in literature. Through the validation experiments of this work the rule of thumb, not to trust TSMs beyond the mean residence time of the substance, has become palpable. Nevertheless TSMs and related methods are computationally fast procedures, which deliver first hints on potential source areas, if applied within the frame of the mean residence time of the considered substance.     

Chemical characteristics of long-range transport aerosol at background sites in Korea

In this study, background concentration sites of Deokjeok and Gosan, which were deemed suitable for monitoring the impact of long-range transported air pollutants, were selected. An investigation of the source types of pollutants, their locations, and relative quantitative contributions to the particulate concentrations at both sites using appropriate methodologies to make initial estimations was conducted. Episodic measurements of PM_2.5, PM₁₀, and size distribution, along with its ion and carbon components were performed from 2005 to 2007, and a comprehensive analysis of the results was conducted utilizing back trajectory analysis. As for frequency of wind direction, it was quite apparent that the two sites are heavily influenced by air masses originating from the eastern and northern regions of China. For PM_2.5 and PM₁₀, the mass concentrations from north and east China were higher than other cases, originating from the ocean. In the northerly-wind case, meteorological properties for Deokjeok and Gosan and the influence of carbon emissions from northwest Korea resulted in a changing of air mass properties during transport. As was the case with mass concentration, the highest contribution for ionic and carbon components of PM_2.5 and PM₁₀ for both sites appeared for the westerly wind case. A specially high relative contribution, greater than 1.4 times, was apparent in the secondary aerosol case because of a large influence of long-range transported pollutants from east China. Carbon components exhibited different behaviors for the northerly and westerly wind cases compared with secondary aerosol. The major reason for this discrepancy appears to be the carbon emissions from northwest Korea.     

Electrical aerosol analyzer: An alternate method for use at high altitude or reduced pressure

To use the Electrical Aerosol Analyzer (EAA) for determining submicron aerosol size distributions at reduced pressure, Yeh et al. (1981) developed a method by modifying the standard data reduction table. Based on the same assumptions i.e., the particle charging is independent of pressure when the charging parameter, Nt, is held constant, an alternative method was developed. A test indicated that these two methods are comparable and the agreement between the two is very good. The advantage of the present method is that all existing EAA data analysis packages or computer programs can be directly applied without any modification.     

Contribution of primary and secondary sources to organic aerosol and PM2.5 at SEARCH network sites

Chemical tracer methods for determining contributions to primary organic aerosol (POA) are fairly well established, whereas similar techniques for secondary organic aerosol (SOA), inherently complicated by time-dependent atmospheric processes, are only beginning to be studied. Laboratory chamber experiments provide insights into the precursors of SOA, but field data must be used to test the approaches. This study investigates primary and secondary sources of organic carbon (OC) and determines their mass contribution to particulate matter 2.5 microm or less in aerodynamic diameter (PM2.5) in Southeastern Aerosol Research and Characterization (SEARCH) network samples. Filter samples were taken during 20 24-hr periods between May and August 2005 at SEARCH sites in Atlanta, GA (JST); Birmingham, AL (BHM); Centerville, AL (CTR); and Pensacola, FL (PNS) and analyzed for organic tracers by gas chromatography-mass spectrometry. Contribution to primary OC was made using a chemical mass balance method and to secondary OC using a mass fraction method. Aerosol masses were reconstructed from the contributions of POA, SOA, elemental carbon, inorganic ions (sulfate [SO4(2-)], nitrate [NO3-], ammonium [NH4+]), metals, and metal oxides and compared with the measured PM2.5. From the analysis, OC contributions from seven primary sources and four secondary sources were determined. The major primary sources of carbon were from wood combustion, diesel and gasoline exhaust, and meat cooking; major secondary sources were from isoprene and monoterpenes with minor contributions from toluene and beta-caryophyllene SOA. Mass concentrations at the four sites were determined using source-specific organic mass (OM)-to-OC ratios and gave values in the range of 12-42 microg m(-3). Reconstructed masses at three of the sites (JST, CTR, PNS) ranged from 87 to 91% of the measured PM2.5 mass. The reconstructed mass at the BHM site exceeded the measured mass by approximately 25%. The difference between the reconstructed and measured PM2.5 mass for nonindustrial areas is consistent with not including aerosol liquid water or other sources of organic aerosol.     

Characterization of PM10 atmospheric aerosol at urban and urban background sites in Fuzhou city, China

Background

PM₁₀ aerosol samples were simultaneously collected at two urban and one urban background sites in Fuzhou city during two sampling campaigns in summer and winter. PM₁₀ mass concentrations and chemical compositions were determined.

Methods

Water-soluble inorganic ions (Cl^?, NO ₃ ^? , SO ₄ ^2? , NH ₄ ⁺ , K⁺, Na⁺, Ca²⁺, and Mg²⁺), carbonaceous species (elemental carbon and organic carbon), and elements (Al, Si, Mg, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, and Pb) were detected using ion chromatography, thermal/optical reflectance, and proton-induced X-ray emission methods, respectively.

Results

PM₁₀ mass concentrations, as well as most of the chemical components, were significantly increased from urban background to urban sites, which were due to enhanced anthropogenic activities in urban areas. Elements, carbonaceous species, and most of the ions were more uniformly distributed at different types of sites in winter, whereas secondary ion SO ₄ ^2? , NO ₃ ^? , and NH ₄ ⁺ showed more evident urban-background contrast in this season. The chemical mass closure indicated that mineral dust, organic matters, and sulfate were the most abundant components in PM₁₀. The sum of individually measured components accounted for 86.9?C97.7% of the total measured PM₁₀ concentration, and the discrepancy was larger in urban area than in urban background area.

Conclusion

According to the principal component analysis?Cmultivariate linear regression model, mineral dust, secondary inorganic ions, sea salt, and motor vehicle were mainly responsible for the PM₁₀ particles in Fuzhou atmosphere, and contributed 19.9%, 53.3%, 21.3%, and 5.5% of PM₁₀, respectively.     

Application and comparison of two statistical trajectory techniques for identification of source regions of atmospheric aerosol species

Two approaches for identification of source locations and preferred transport pathways of atmospheric particulate trace elements and aerosol species are investigated, namely, versions of the potential source contribution function method (PSCF) and the concentration field method (CF). Both methods are based on combining chemical data with calculated air parcel backward trajectories. The two methods are applied to four multi-species multi-annual concentration time series measured at sites in Finland, Norway, and Israel. A non-parametric bootstrap technique is used to estimate the statistical significance of the calculated PSCF values. It is found that the methods agree well with each other and correctly identify known emission sources. Examples of applying the methods are presented, mainly for the site in Finland.     

Trends and sources of particulate matter in the Superstition Wilderness using air trajectory and aerosol cluster analysis

Ambient aerosols adversely affect human health and visibility and impact climate. Identification of sources of particulate matter and its precursors is necessary for developing control strategies. The goal of this research is to utilize long-term speciated particulate matter data and back-trajectory cluster analyses to determine trends and sources of particulate matter in the Superstition Wilderness, a rural area east of Phoenix, Arizona. Twenty-four hour back-trajectories were calculated for every hour of every 24-h particulate matter sample obtained by IMPROVE from 1991 to 2004. Days that included back-trajectories with considerable spatial variance were excluded from further analyses. To minimize uncertainties inherent in single trajectories, all calculated trajectories for each sampling day were averaged to represent the air mass sampled during that day. Cluster analysis of trajectories identified four unique regions, including a region with Phoenix, a region with copper smelters, and one with coal-fired power plants. Yearly averages of sulfate, nitrate, soil, and carbon concentrations were calculated for each region. Statistically significant trends in species concentrations by region and independent of region and differences in concentrations between regions were examined.Sulfate concentrations from the region with smelters were higher than other regions but decreased during the study period. Emissions data from the smelters indicate that much of the sulfate from the region was due to the smelters. The overall 2.2% year⁻¹ decrease in sulfate concentrations at TNM is likely due to decreased emissions from the copper smelters. A 3.6% year⁻¹ increase in nitrate concentrations was driven largely by increasing NO_x concentrations from Phoenix and to a lesser extent the region southwest of the site which includes Tucson and suburban/urban areas between Phoenix and Tucson. Soil concentrations were higher from regions with deserts than the region without desert. This method could not identify trends or source regions of carbonaceous aerosols at this site.     

Interactions of carbon monoxide and hemoglobin at high altitude

The health risks to U.S. populations who are exposed to ambient carbon monoxide and live at altitudes (such as Denver, Salt Lake City and Albuquerque) were evaluated using a set of mathematical models. The assumption that a given increase in carboxyhemoglobin would require a more stringent volumetric air quality standard was tested. The results using the model predict that the 8-h or 1-h standards adopted for sea level conditions need not be altered to protect individuals against health risks at altitude, if the standards are in volumetric terms. They would need to be reduced if the standards are left in gravimetric terms. If the guideline is to be based on a given decrement of oxygen tension, many other variables must be specified, but expected differences in ambient carbon monoxide have a small impact compared to the effect of altitude itself.     

Identifying the effect of individual emissions sources on particulate air quality within a photochemical aerosol processes trajectory model

A procedure is demonstrated that greatly expands the number of sources whose contribution to ambient particle levels can be followed separately within an aerosol processes trajectory model without significantly increasing the computational burden of the problem. Particles emitted from different sources within the same general class can be differentiated from each other with this technique; for example particles emitted by on-road diesel vehicles can be distinguished from particles emitted by diesel railroad locomotives, and particles emitted from identical sources at different locations can be distinguished from each other as well. The method developed is illustrated by application to the air quality situation in Southern California. The contributions of more than 50 types of air pollution sources to primary particle concentrations at Claremont, CA, are separated from each other by post-processing the output from the aerosol processes trajectory model for an externally mixed aerosol developed previously by Kleeman and Cass (1998, Atmospheric Environment 32, 2803–2816; 1999 Environmental Science and Technology, 33, 177–189).     

Persistent organochlorine compounds in soils and sediments of European high altitude mountain lakes

The composition of persistent organochlorine compounds (OC) in soils and sediments from two high altitude European mountain lakes, Redon in the Pyrenees and Ladove in the Tatra mountains, has been studied. Sediment cores from two additional lakes in the Tatra mountains, Starolesnianske Pleso and Dlugi Staw, have also been examined. DDTs (1.7-13 ng g(-1)) were the most abundant OC in soils followed by total polychlorobiphenyls (PCBs; 0.41-1.5 ng g(-1)) and hexachlorobenzene (HCB; 0.15-0.91 ng g(-1)). In sediments, the dominant OC were also DDTs (3.3-28 ng g(-1)) and PCBs (2.3-15 ng g(-1)). These concentrations are low, involving absence of major pollution sources in these high mountain regions. The downcore OC profiles in soils and sediments were similar but higher concentrations and steeper vertical gradients were observed in the latter. Radiometric determinations showed absence of significant OC transport from catchment to lake. The sediment-soil difference points therefore to a better retention of the OC load in sediments than soils which may be related to the low temperatures that are currently encountered at the bottom of the lake water column and the depletion of sediment bioturbation in these cold environments. Significant qualitative changes in the soil PCB distributions are observed downcore. These involve a dominance of the high molecular weight congeners in the top core sections and those of lower weight (i.e. less chlorinated) in the bottom. Anaerobic dechlorination of higher molecular weight congeners occurring in microsites, e.g. as observed in flooded or poorly drained soils, could be responsible for these changes. This process could be concurrent to bioturbation.     

Comparison of multi-receptor and single-receptor trajectory source apportionment (TSA) methods using artificial sources

Two trajectory source apportionment methods were tested using an artificially generated data set to determine their ability to detect the known sources. The residence time or conditional probability method developed by Ashbaugh et al. [1985. A residence time probability analysis of sulfur concentrations at Grand Canyon National Park. Atmospheric Environment 19(8), 1263–1270] uses a single receptor at a time, whereas the new multi-receptor (MURA) method developed here uses several receptors at once in an attempt to detect the sources with higher accuracy. The methods were first tested using a simulation with a single source and then with another simulation using four sources. The ability of the methods to detect the sources was quantified for each simulation. The MURA trajectory method proved to be superior at identifying sources for these simulations.     

Comparisons of coarse-mode aerosol nitrate and ammonium at two polluted coastal sites

Direct atmospheric fixed-nitrogen deposition can contribute to eutrophication in coastal and estuarine waters and can be enhanced by heterogeneous reactions between gaseous atmospheric nitrogen species and aerosol sea salt, which increase deposition rates. Size-segregated aerosol samples were collected from two coastal sites: Weybourne, England and Mace Head, Ireland. Major-ion aerosol concentrations were determined and temporal patterns were interpreted with the use of air-mass back trajectories. Low levels of terrestrially derived material were seen during periods of clean, onshore flow, with respective concentration ranges for nitrate and ammonium of 0.47–220 and below detection limit to 340 nmol m⁻³. Corresponding levels of marine derived material during these periods were high, with sodium concentrations ranging from 39 to 1400 nmol m⁻³. Highest levels of terrestrially derived material were seen during polluted, offshore flow, where the air had passed recently over strong source regions of the UK and northern Europe, with concentration ranges of nitrate and ammonium of 5.6–790 and 9.7–1000 nmol m⁻³, respectively. During polluted flow ∼40–60% of the nitrate was found in the coarse mode (>1 μm diameter) and under clean marine conditions almost 100% conversion was seen. In addition, our data suggests strong evidence for dissolution/coagulation processes that also shift nitrate to the coarse mode. Furthermore, such processes are thought also to give rise to the size-shifting of aerosol ammonium, since significant coarse-mode fractions of this species (∼19–45%) were seen at both sites. A comparison of the relative importance of nitrate and ammonium in the overall dry deposition of inorganic fixed-nitrogen at each site indicates that at Weybourne the mass-weighted dry deposition velocity of the latter is around double that seen at Mace Head with its resultant contribution to the overall inorganic nitrogen dry flux exceeding that of nitrate.     

Analysis of rainfall and fine aerosol data using clustered trajectory analysis for National Park sites in the Western US

We calculated daily back-trajectories using the NOAA-HYSPLIT model to analyze 7 years of precipitation and PM2.5 data from three National Park sites in the Western US. Using a k-means clustering algorithm, the trajectories were segregated into six main transport patterns. At each site, we calculated trajectory clusters for 1, 5, and 10 days to represent short, medium and long-range flow patterns. Most clusters show marked seasonality. Faster flow patterns are more prevalent in winter, and slower/stagnant patterns are more prevalent in summer. The analyses between the 1, 5, and 10-day clusters revealed that the clusters of different duration show very different predictive power for rainfall and PM2.5. We found that the 1-day clusters are a better predictor for precipitation and PM2.5 concentrations, followed by the 5-day clusters. The 10-day clusters did a poorer job of differentiating precipitation and PM2.5. This is because the 10-day clusters show the greatest variability during the first day or two of transport.     

Models and statistical methods for gaseous emission testing of finite sources in well-mixed chambers

Two families of mathematical models are proposed to represent either the concentration of a gaseous emission in or the accumulated amount exiting from a well-mixed, environmentally controlled test chamber. A thin film model, which seems applicable to such sources as carpet adhesive, etc., has the capability of isolating the true emission rate constant from chamber effects. It has successfully modeled emissions of methyl ethyl ketone, a C₈ alcohol, and butyl propionate from latex caulk. Chamber effects in the form of temporary wall retention were identified for the latter two compounds. An analogous, deep source, diffusionlimited model for plywood, etc., once fitted to a data set, can be used to generalize to other combinations of source surface area, chamber volume, and air exchange rate.     

Investigation of sources of atmospheric aerosol at a hot spot area in Dhaka, Bangladesh

Samples of fine and coarse fractions of airborne particulate matter were collected at the Farm Gate area in Dhaka from July 2001 to March 2002. Dhaka is a hot spot area with very high pollutant concentrations because of the proximity of major roadways. The samples were collected using a "Gent" stacked filter unit in two fractions of 0- to 2.2-microm and 2.2- to 10-microm sizes. The samples were analyzed for elemental concentrations by particle-induced X-ray excitation (PIXE) and for black carbon by reflectivity methods, respectively. The data were analyzed by positive matrix factorization (PMF) to identify the possible sources of atmospheric aerosols in this area. Six sources were found for both the coarse and fine PM fractions. The data sets were also analyzed by an expanded model to explore additional sources. Seven and six factors were obtained for coarse and fine PM fractions, respectively, in these analyses. The identified sources are motor vehicle, soil dust, emissions from construction activities, sea salt, biomass burning/brick kiln, resuspended/fugitive Pb, and two-stroke engines. From the expanded modeling, approximately 50% of the total PM2.2 mass can be attributed to motor vehicles, including two-stroke engine vehicle in this hot spot in Dhaka, whereas the PMF modeling indicates that 45% of the total PM2.2 mass is from motor vehicles. The PMF2 and expanded models could resolve approximately 4% and 3% of the total PM2.2 mass as resuspended/fugitive Pb, respectively. Although, Pb has been eliminated from gasoline in Bangladesh since July 1999, there still may be substantial amounts of accumulated lead in the dust near roadways as well as fugitive Pb emissions from battery reclaimation and other industries. Soil dust is the largest component of the coarse particle fraction (PM2.2-10) accounting for approximately 71% of the total PM2.2-10 mass in the expanded model, whereas from the PMF modeling, the dust (undifferentiated) contribution is approximately 49%.     

Regional aspects and statistical characterisation of the load with semivolatile organic compounds at remote Austrian forest sites

Spruce needles and humus layer of 25 remote forest sites spread all over Austria were investigated for their concentrations of PCDD/F, PCB, HCH, HCB, PCP, DDX and PAH. Influences of the sites' location on the detected concentrations have been identified: The north of Austria was characterised by a comparably higher overall pollutant load. In addition, altitudinal aspects were addressed. Between several compounds significant positive correlations have been identified, which were more pronounced for compounds with a stronger causal relationship. Pattern analyses allowed to identify--even for the remote sites--differences between the relative PCDD/F, HCH, DDX and PAH patterns of the sites. Partly, these different patterns were related to significantly higher or lower corresponding absolute concentrations of the sites.     

Long-term measurements and model calculations of formaldehyde at rural European monitoring sites

Several years of formaldehyde measurements at six rural European sites are compared with EMEP oxidant model calculations. The model results agree well with the measured values both with regard to average seasonal cycles as well as on an episodic day-to-day basis at all sites except for Ispra in Northern Italy. For several of the sites the agreement is better during the summer months whereas the model underestimates the concentrations in winter. The model results show that formaldehyde in summer is mainly controlled by photochemical processes such as reaction with OH, photolysis and formation through NO+peroxy radicals. Furthermore, in spite of the short chemical lifetime of formaldehyde in summer, emission pulses of volatile organic compounds (VOC) and isoprene influence formaldehyde concentrations even 48 h after the emission. These results indicate that formaldehyde is well suited for validating photochemical transport models on a long-range (European) scale. Furthermore, the reasonable agreement between model calculations and measurements for carbonyls presented here, combined with previous findings for non-methane hydrocarbons (NMHC) and evaluation of the condensed EMEP chemical mechanism against a detailed Master chemical mechanism gives encouraging support that the EMEP model describes the main ozone-forming photochemical processes in a reasonable way.